Manufacture of negative plates



Patented Oct. 20, 1953 MANUFACTURE OF NEGATIVE-PLATES William D. Carson and Alva :L. Hindall, Muneie, Ind., assignors to General Motors Corporation, Detroit, Mich., a. corporation of Delaware I No Drawing. ApplicatinuJune28, 951,

Serial No. 234,164

. 1 This inventlonrelates to storage batteries and isparticularly concerned with a method'ior the accelerated aging of negative pasted plates for usein said storage batteries.

In our copending application Serial No. 234,032, filed concurrently herewith, a method for curing positive pasted plates is disclosed. The present invention is directed to a method for effecting a satisfactory cure of thenegative pasted plates.

It is, therefore, the basic object of this invention to'provide a method of curing pasted negative plates wherein the product is uniform and extremely rugged and wherein the cure is efiected in a reduced'time period over prior art processes. In carryingout the above object, it is a further object of the invention to provide a method for accelerated aging of negative plates, under steam pressure, wherein the pressure and temperature *are'controlled for obtaining the desired results.

A stillfurther object of the invention is to provide a method for pressure curing the negative pasted plate-wherein the ruggedness of the plate is obtained by actually bonding the active material of the grid paste onto the grid aswill be explained hereinafter. V

Further objects and advantages of the present invention will be apparent from the following description. 7 V

In our copending application SerialNo. 234,032,

a curing process is set forth wherein pasted plates are cured in a controlled volume oven to reduce the moisture content 'of the plateand to oxidize some of the metallic lead. V The plates, after curing, have about 9% moisture therein which is not a critical figure' from the curing standpoint but which is a desired figure for com mercial operations as discussed in detail in'said copending' application. I

In the present invention, the negative plates are treated in the same manner.

yellow'litharge and metallic lead in the ratio of about 30 to 45 to 25 and'sulphuric acid. 'Th-is paste, after mixing, includes about 30%' red litharge, 55% of colloidal or semi-colloidal lead compounds believed to be basic lead sulphate and hydrated lead compounds and about "15% metallic lead. The pasted plate is then cured by the method *disclosed in" the copending application..Serial No. 234,032. After the cure, it has about 35% with a drop in metallic lead to about 10%, basic lead sulphate 40% and hydrated lead compounds*%. Plates coming out of this cure run about 9% moisture which makes them suit 5 Claims. (01(13633) These plates 40 1 are pasted with a starting mixture of red litharge,

break-apart since the plates are generally-cured in double sections. Theseplates'are, therefore, thestarti'ng point 'of'the present process. In this process, we-age these cured platesto obtain 'a' reduction' in moisture content to approximately i This maybe done'in air-or under accelerated conditions, butwe preferthe air'aging'because of cost. In this connection, we merely stack the'broken apart plates having 10 a 9% moisture on a skid and permit them to stand'in air for about24 'hours or until the moisture content has dropped to approximately -"4 Obviously, thisperio'd will-vary in accordance-with ambient temperature andhu- 'midity but under normal-conditionsa24 hour age will bring :themoisture content to the desired'figure. 'During this aging, the red litharge increases to about-40%,the'basic lead sulphate and :hydrated a lead compounds remain the same and the metallic lead drops to :a' figure of 5%.

In this connection. it should be understood ;-that all the figures given may vary :slightly, these examples --mere1-y being illustrative 1 of a pasted "platecured'and-aged under the optimum condi- 25 :tions. These aged plates-are-next pressure cured can autoclave; The pressure and timevary inversely. weifindthat a.30 minute cure at pound steam pressure -y-ields highlysatisfactory results. However, if the pressure is dropped to 30 .i5gpounds, the time required -,is 32 7 hours -whereas the pressure is increased to 60 pounds, the :time. isreducedtO-G minutes. Thus weare, not limited toanyuspecific pressure and time other .thanthe fact that .the curegmustbe in steam under pressur e and for a time sufficient to obtain the desired results which are a reformation of "yellow litharge 'which comes; about through re- "action-orthe hydrated leadcompounds. Thus the Iormula ofthe pressure cooked paste reyellow litharge, 40% basic lead sulphatein col- "loi'da'l formi-and 5: %metallic lead. I. I The increased ruggedness of the pressure cured negative :plate z-paste may be explained as fol- 5 lows: Thepressure curing of'theplate paste -re- =Sll1tS ll1EimplGV6d :adhesionbetween the pasted 'materialan'dfthegrid. "This isexplained by the fast that the basic': lead sulphate actually attacks the grid-material (usually lead or lead alloys,

such a lead-antimony alloys), thus formin -a-n .been found that the red litharge increases to" g actual-'cheniicalbond between the paste and the grid. The high temperature used in the pressure cure -accelerates this reaction and-the steam which is present prevents the active "material v V from drying out and thus maintains a moist able for stacking and sufficiently rugged for alkaline-condition which-aids inthe gridcoflosolves itself to'about 40% red litharg'e, 15%

sion, thereby resulting in the strong adhesion. Furthermore, the pressure cooking of the negative plate actually causes a recrystallization of the yellow litharge which appears to be another cause for the extreme ruggedness of the plate since this recrystallization results in an interlocking of crystal grains or a difiusion of one crystal into another across grain boundaries to form a mechanical bond or interlock.

From the foregoing, it will be seen therefore that the steam cured negative plate paste is mechanically locked together by the recrystallizd yellow litharge and is chemically adhered to the surface of the grid by the reaction of the basic lead sulphate and the grid material. These induced conditions are believed to be the reason for the extreme ruggedness of the negative plate when cured by the method disclosed herein. This method provides a very improved plate over prior art plates wherein no pressure cure is utilized since we believe that in these prior art plates,

' assumption to a large extent.

Further, the exact percentages may vary according to reaction efiiciency and conditions,

however, the figures noted are examples of a typical reaction in the processes set forth.

While the embodiments of the present invention as herein disclosed, constitute preferred forms, it is to be understood that other forms might be adopted.

What is claimed is as follows:

1. In a method for curing negative pasted plates wherein the initial paste consists of a mixture of red litharge, basic lead sulphate, hydrated lead compounds and metallic lead pasted onto a lead alloy grid and wherein the paste mixture has an initial moisture content of about 13%, the steps comprising; heating the plate in a confined space so that the paste is soaked in a moisture ladened atmosphere provided by moisture being driven from the plate paste, progressively increasing the temperature of heat to a point that the plate paste is reduced in moisturecontent to about 9%, aging the plates in air for a time sufficient to reduce the moisture content to about ai and then pressure curin the plates in a closed chamber with steam under pressures ranging from 5 to 60 pounds per square ch and for --a time ranging from 32 hours to 6 minutes for forming a strong and rugged plate.

2. In a method for curing negative pasted plates wherein the initial paste consists of a mixture of red litharge, basic lead sulphate, hydrated -lead compounds and metallic lead pasted onto a lead alloy grid and wherein the paste mixture has an initial moisture content of about 13%, the steps comprising; soaking the plate in a confined space and under progressively increasing temperatures until the plate paste is reduced in moisture content to about 9% and then aging the plates in air for a time sufhcient to reduce the moisture content to about l and then pres- 1 sure curing the plates in a closed chamber with steam under pressures ranging from 5 to 60 poundsper square inch and for a time ranging from 32 hours to 6 minutes for forming a. strong and rugged plate.

3. In a method for curing negative pasted plates wherein the initial paste consists of a mixture of red litharge, basic lead sulphate, hydrated lead compounds and metallic lead pasted onto a lead alloy grid and wherein the paste mixture has an initial moisture content of about 13%, the steps comprising; soaking the plate in a confined space and under progressively increasing temperatures until the plate paste is reduced in moisture content to about 9%, aging the plates for a time suflicient to reduce the moisture content to about 4 wherein the aging takes place in air, and then curing the plates in a closed chamber with steam at a pressure of about 30 pounds per square inch and for a period of about thirty minutes for recrystallizing yellow litharge from a portion of the platepaste and for causing a reaction between the paste and the grid for firmly adhering the paste to the grid. s

4. In a method for curing negative pasted plates wherein the initial paste consists of a mixture of red litharge, basic lead sulphate, hydrated lead compounds and metallic lead .pasted onto a lead alloy grid and wherein the paste mixture has an initial moisture content of about 13%, the steps comprising; heating the plate in a confined space so that the paste is soaked in a moisture ladened atmosphere provided by moisture being driven from the plate paste, progressively increasing the temperature of heat to a point that the plate paste is reduced in moisture content to about 9%, aging the plates for a time suflicient to reduce the moisture content to about l wherein the aging takes place in air, and then curing the plates in a closed chamber with steam at a pressure of about 30 pounds per square inch and for a period of about thirty minutes for recrystallizing yellow litharge from a portion of the plate paste and for causing a reaction between the paste and the grid for firmly adhering the paste to the grid. 5. In a method for curing negative pasted plates wherein the initial paste consists of a mixture of red litharge, basic lead sulphate, hydrated lead compounds and metallic lead pasted onto a lead alloy grid and wherein the paste mixture has an initial moisture content of about 13%, the steps comprising; heating the plate in a confined space so that the paste is soaked in a moisture ladened atmosphere provided by moisture being driven from the plate paste, progressively increasing the temperature of heat to a point that the plate paste is reduced in' moisture content to about 9%, aging the plates in air for a time sufiicient to reduce the moisture, content to about 1%;%, and then heating the plates in steam under pressure and .for atime and at a temperature suificient to recrystallize yellow litharge in the plate paste and simultaneouslyto cause a chemical reaction between the basic lea sulphate and the grid. WILLIAM D. CAR-SON.

ALVA L. HINDALL..,

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,481,2 8 Hindall Sept. 6, 1949 2,553,192 Hindall May 15, 1951 OTHER REFERENCES Transactions'of Electrochemical Society, vol. 69 (1936), pages 233-242. 

2. IN A METHOD FOR CURING NEGATIVE PASTED PLATES WHEREIN THE INITIAL PASTE CONSISTS OF A MIXTURE OF RED LITHARGE, BASIC LEAD SULPHATE, HYDRATED LEAD COMPOUNDS AND METALLIC LEAD PASTED ONTO A LEAD ALLOY GRID AND WHEREIN THE PASTE MIXTURE HAS AN INITIAL MOISTURE CONTENT OF ABOUT 13%, THE STEPS COMPRISING; SOAKING THE PLATE IN A CONFINED SPACE AND UNDER PROGRESSIVELY INCREASING TEMPERATURES UNTIL PLATE PASTE IS REDUCED IN MOISTURE CONTENT TO ABOUT 9% AND THEN AGING THE PLATES IN AIR FOR A TIME SUFFICIENT TO REDUCE THE MOISTURE CONTENT TO ABOUT 4 1/2 AND THEN PRESSURE CURING THE PLATES IN A CLOSED CHAMBER WITH STEAM UNDER PRESSURES RANGING FROM 5 TO 60 POUNDS PER SQUARE INCH AND FOR A TIME RANGING FROM 32 HOURS TO 6 MINUTES FOR FORMING A STRONG AND RUGGED PLATE. 